JP2624711B2 - New polyester carbonate and its production method - Google Patents

Description

The present invention relates to a novel polyester carbonate and a method for producing the same, and more particularly, to a polyester resin suitably used in the field of resin materials such as optical device materials and various industrial materials. To a novel polyester carbonate and a method for producing the same.

[Conventional technology]

Polyester carbonate is excellent in transparency and rigidity, heat resistance can be set widely by changing the ester content, it is a polymer excellent in practical use, and it is widely used as a resin material for various industrial materials. It is used for Conventionally known polyester carbonates include those having the following two types of repeating units obtained by reacting a mixture of bisphenol A, terephthalic acid chloride, and isophthalic acid chloride with phosgene.

However, with the diversification of uses of plastic products in recent years, there has been a demand for polyester carbonates having more excellent properties in addition to the above-mentioned excellent properties of conventional polyester carbonates.

For example, materials for optical devices such as lenses, prisms, audio disks, and optical memory disks are required to have various performances in addition to transparency, heat resistance, and mechanical strength. It is required that the photoelastic coefficient is small as a characteristic. If the photoelastic coefficient is large,
As a result, the birefringence increases, and the read sensitivity of the information recorded on the disc is lowered, and errors occur. Further, when used as a material for a plastic container, it is particularly required to have low water absorption.

[Problems to be solved by the invention]

The present invention is, firstly, excellent in transparency, mechanical strength, heat resistance, and has a low photoelastic coefficient, is useful as a material for optical devices, and has low water absorption, and is suitably used as a material for containers and the like. The purpose is to provide a new polyester carbonate that can be used.

The second object of the present invention is to provide a suitable method for producing the above-mentioned novel polyester carbonate of the present invention.

[Means for solving the problem]

The present invention has the general formula And a general formula represented by (Wherein X is a single bond, an ether bond, a thioether bond, -SO _2- , Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n is 2
And p is an integer of 4 to 8. The present invention provides a novel polyester carbonate having a methylene chloride solution having a concentration of 0.5 g / dl and a reduced viscosity [η _sp / c] at 20 ° C. of 0.3 to 2.0 dl / g.

Further, a second invention is a method for producing the above-mentioned novel polyester carbonate, which has a general formula (Wherein X is a single bond, an ether bond, a thioether bond, -SO _2- , Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n is 2
And p is an integer of 4 to 8. By reacting a bisphenol compound represented by the formula (I) with isophthalic acid halide and / or terephthalic acid halide and phosgene; And a general formula represented by (Wherein X has the same meaning as described above), and the reduced viscosity [η _sp / c] of the methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C. is 0.3 to 2.0 dl. / g of a novel polyester carbonate.

X in the repeating unit represented by the general formula (I) in the polyester carbonate of the present invention may be the same or different.
The Y, a single bond, an ether bond, a thioether bond, -SO ₂ -, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, decylene group, ethylidene group, 1,1-propylidene group, 1 -Phenyl-1,1-methylene group, 2,2-propylidene group, 2,2-
Butylidene group, 3,3-pentylidene group, 1-phenyl-
1,1-ethylidene group, cyclohexylidene group, cyclopentylidene group, 2,2-octylidene group, diphenylmethylene group and the like are preferable, and in particular, 2,2-propylidene group, 1-phenyl-1,1- An ethylidene group, and -SO _2-
Is preferred.

The average molecular weight of the polyester carbonate of the present invention can be appropriately selected according to the type of optical equipment. The reduced viscosity [η _sp / c] of the methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C. [η _sp / c] is 0.3 to 2.0 dl. / g, preferably 0.35 to 2.
It is 0dl / g. If the reduced viscosity is less than 0.3 dl / g, the mechanical strength of the molded article may be low, and 2.0 d
If it exceeds l / g, sufficient fluidity may not be obtained, distortion may occur during processing, and an optically uniform molded article may not be obtained.

When the mole fraction of the repeating unit (I) is x and the mole fraction of the repeating unit (II) is y, x / (x
+ Y) is preferably in the range of 0.01 to 0.99.
If this value is less than 0.01, the effect of lowering the photoelastic coefficient may not be obtained, and if it exceeds 0.99, the fluidity may be reduced.

Further, in the polyester carbonate of the present invention, the general formula And the general formula And a repeating unit represented by the formula: Among them, those in which the ratio of the repeating units represented by the general formulas (IV) and (V) is 10/90 to 90/10 are particularly preferable. If this ratio deviates from the above range, the molded product may become brittle.

The polyester carbonate of the present invention can be produced by various methods, and among them, it can be suitably produced by the above-mentioned production method of the present invention.

 Hereinafter, the production method of the present invention will be described in detail.

The method for producing the polyester carbonate of the present invention comprises reacting at least one bisphenol compound represented by the general formula (III), isophthalic acid halide and / or terephthalic acid halide, and phosgene.

The bisphenol compound of the general formula (III) used in the production method of the present invention includes, for example, 3,3'-diphenyl-4,4'-dihydroxybiphenyl, bis (3-
Phenyl-4-hydroxyphenyl) ether, bis (3-phenyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) methane, 2-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,3-bis (3-phenyl-4-
Hydroxyphenyl) propane, 1,4-bis (3-phenyl-4-hydroxyphenyl) butane, 1,6-bis (3-phenyl-4-hydroxyphenyl) hexane,
1,8-bis (3-phenyl-4-hydroxyphenyl)
Octane, 1,10-bis (3-phenyl-4-hydroxyphenyl) decane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ) Propane, 1,1-bis (3
-Phenyl-4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) butane, 3-bis (3-phenyl-4-hydroxyphenyl) pentane, 1,1-bis (3
-Phenyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-phenyl-
4-hydroxyphenyl) cyclopentane, 2,2-bis (3-phenyl-4-hydroxyphenyl) octane,
Diphenyl-bis (3-phenyl-4-hydroxyphenyl) methane and the like can be mentioned.

Among these, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane,
And bis (3-phenyl-4-hydroxyphenyl)
Sulfone is preferred.

In the production method of the present invention, it is preferable to use an isophthalic halide and a terephthalic halide in combination. At that time, it is particularly preferable that the ratio between the isophthalic acid component and the terephthalic acid component is 10/90 to 90/10 by mol%. Outside of this range, when the resulting resin is molded, the molded article may become brittle.

Isophthalic acid chloride is preferable as the isophthalic acid halide, and terephthalic acid chloride is preferable as the terephthalic acid halide.

An example of a preferred embodiment of the production method of the present invention will be described below.

(1) First, a bisphenol compound of the general formula (III) is dissolved in an aqueous alkali solution such as an aqueous potassium hydroxide solution and reacted with almost twice the molar amount of phosgene in a solvent such as methylene chloride. An oligomer having a chloroformate end is produced. Reaction temperature is usually 5-40 ° C
The reaction time is usually 5 to 30 minutes, and the reaction is carried out under normal pressure or a slight pressure. Although the degree of polymerization of this oligomer is not particularly limited, it is usually preferably 2 to 10.

(Where a represents the degree of polymerization.) (2) On the other hand, the bisphenol compound of the general formula (III) is dissolved in a water-immiscible solvent such as methylene chloride, carbon tetrachloride, chloroform and the like, and isophthalic halide and / or
Alternatively, a terephthalic acid halide is dissolved in an aqueous alkali solution such as an aqueous potassium hydroxide solution, and the both solutions are mixed and reacted to produce an oligomer having a hydroxyl group terminal represented by the following general formula. The reaction temperature is usually from 5 to 40 ° C., the reaction time is usually from 5 to 50 minutes, and the reaction is carried out under normal pressure or slight pressure. Since this reaction is an exothermic reaction, it is desirable to carry out the reaction while cooling with ice. Although the degree of polymerization of this oligomer is not particularly limited, it is usually preferably 2 to 10.

(In the formula, b represents the degree of polymerization.) At this time, the used molar amount of the bisphenol compound is made larger than the used molar amount of the dicarboxylic acid halide.

Further, as the raw material bisphenol compound for producing the oligomer represented by the general formula (VII), it is also possible to use a different kind of bisphenol compound from the raw material bisphenol compound for producing the oligomer represented by the general formula (VI).

(3) Next, a solution obtained by dissolving the oligomer of the general formula (VI) in a solvent such as methylene chloride is added to the reaction solution containing the oligomer having a hydroxyl group terminal of the general formula (VII), and the reaction is carried out. Synthesize polyester carbonate. It is desirable to add a catalyst such as triethylamine in order to promote the polycondensation reaction. If the obtained reaction product is poured into a large amount of a precipitant such as methanol,
The polyester carbonate of the invention precipitates. The reaction temperature is usually from 5 to 40 ° C., the reaction time is usually from 10 to 120 minutes, and the reaction is carried out under normal pressure or slight pressure.

In order to control the degree of polymerization, it is desirable to add a molecular weight regulator such as a monovalent phenol such as o-phenylphenol, pt-butylphenol and nonylphenol. The molecular weight regulator is (1), (2),
It can be added in any of the steps (3). Further, a monovalent acid chloride such as benzoic acid chloride may be added at the stage of (2) and / or (3).

The polyester carbonate thus obtained is excellent in transparency, mechanical strength and heat resistance, and has a small photoelastic coefficient and low anisotropy, and is useful as a material for optical equipment. Memory disks, still cameras, video cameras, telescopes,
Useful for eyeglasses, contact lenses, prisms, optical fibers, etc. Further, it has low water absorption and is useful as a material for various molded articles such as a material for a container.

The novel polyester carbonate of the present invention is a method usually used for molding polyester carbonate,
For example, molding can be performed by injection molding, extrusion molding, blow molding, or the like, and a commonly used molding apparatus can be applied.

In the above-mentioned molding method, the polyester carbonate of the present invention may be molded as it is, but if necessary, an antioxidant, a flame retardant, an ultraviolet absorber, an antistatic agent, a lubricant, a coloring agent, etc. are usually added to the polyester carbonate. Additives to be added.

As the antioxidant used, for example, 2,6-di-
t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,
2'-methylene-bis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-
Butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1 Phenolic compounds such as 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, and amine-based compounds such as phenyl-β-naphthylamine and N, N′-diphenyl-p-phenylenediamine Compound, tris (nonylphenyl)
Phosphorus compounds such as phosphite, triphenylphosphite, trioctadecylphosphite, diphenylisodecylphosphite, sulfur compounds such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, etc. No.

Examples of the flame retardant used include halogen-based flame retardants such as polybromobutylene, decabromodiphenyl ether, and tetrabromobisphenol A; and phosphorus-based flame retardants such as ammonium phosphate, tricresyl phosphate, triethyl phosphate, and acid phosphate. And inorganic flame retardants such as tin oxide and antimony trioxide.

Examples of the ultraviolet absorber used include, for example, salicylic acid-based ultraviolet absorbers such as phenyl salicylate and pt-butylphenyl salicylate, and benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Agent, 2- (2'-
Benzotriazole-based ultraviolet absorbers such as hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole;

Examples of the antistatic agent used include, for example, nonionic antistatic agents such as polyoxyethylene alkylamine and polyoxyethylene alkylamide, anionic antistatic agents such as alkyl phosphonate and alkylbenzene sulfonate, and quaternary ammonium chloride. Examples include cationic antistatic agents such as quaternary ammonium sulfate, and amphoteric antistatic agents such as alkyl betaine type and alkyl imidazoline type.

Examples of the lubricant used include lubricants such as aliphatic hydrocarbons, higher aliphatic alcohols, fatty acid amides, metal soaps, and fatty acid esters.

As a coloring agent to be used, a usual coloring agent used for coloring a plastic can be used.

Further, upon molding, the polyester carbonate of the present invention further includes other components such as phosphites for preventing coloring and deterioration of transparency, and a plasticizer for increasing a melt index value. be able to.

Examples of the phosphites used in this case include tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trisstearyl phosphite, triphenyl phosphite, tricresyl phosphite, and tris ( Nonylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di-2
-Ethylhexyl phosphite, phenyldidecyl phosphite, tricyclohexyl phosphite, distearyl pentaerythrityl diphosphite, diphenylpentaerythrityl diphosphite and the like.

Examples of the plasticizer include alkyl phthalates such as 2-ethylhexyl phthalate, n-butyl phthalate, isodecyl phthalate, tridecyl phthalate, heptyl phthalate and nonyl phthalate; and 2-ethylhexyl adipate and 2-ethylhexyl sebacate. Alkyl esters of basic acids, alkyl phosphates such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate, etc., and low aliphatic epoxy esters such as epoxidized octyl oleate and epoxidized butyl oleate. Or polyester-type plasticizers, chlorinated fatty acid esters, and the like.

Further, other resins may be blended and molded as long as the properties of the polyester carbonate of the present invention are not impaired.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example 1 95.0 g (0.25 mol) of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane was dissolved in 650 ml of a 1.5 N aqueous potassium hydroxide solution, and 250 ml of methylene chloride was added.
Phosgene gas was blown at a rate of 1000 ml / min with vigorous stirring. When the pH reached 10, the supply of phosgene was stopped, the mixture was allowed to stand, and the degree of polymerization having a chloroformate terminal was 2 to 2.
A methylene chloride solution of the oligomer of 10 was obtained.

On the other hand, 10.15 g (0.05 mol) of isophthalic acid chloride,
Dissolve 10.15 g (0.05 mol) of terephthalic acid chloride in 100 ml of methylene chloride, add a 2N potassium hydroxide solution of 57 g (0.15 mol) of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, and stir. The reaction was carried out below. The reaction was performed while cooling with ice water. After the reaction for 5 minutes, 300 ml of a methylene chloride solution of the oligomer having a chloroformate terminal obtained above was added, and 1.0 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst, and the mixture was reacted for 1 hour with vigorous stirring.

After the reaction, the reaction solution was diluted with methylene chloride 1 and water was added.
Washing was performed in the order of a 01N aqueous potassium hydroxide solution, water, and 0.01N hydrochloric acid. The obtained methylene chloride solution was poured into methanol injection of 5, and the polyester carbonate was recovered.
The obtained polyester carbonate was dried at 80 ° C. under reduced pressure for 24 hours. As a result of infrared absorption spectrum analysis, 1750 cm
Located in the absorption by an ester bond of ^-1 were observed absorption by carbonate linkage position of 1650 cm ^-1. Also, NM
From the results of R analysis, it was confirmed that the obtained polyester carbonate had the following repeating units.

The reduced viscosity [ηsp / c] of the obtained polyester carbonate in methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C.
It was 0.50 dl / g.

The table shows the glass transition temperature, photoelastic coefficient, and moisture permeability of this polyester carbonate.

Example 2 Example 2 was repeated except that 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane was used instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane. By performing the same operation as in Example 1, a polyester carbonate having the following repeating units was obtained.

The reduced viscosity [ηsp / c] of the obtained polyester carbonate in methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C.
It was 0.55 dl / g.

The table shows the glass transition temperature, photoelastic coefficient, and moisture permeability of this polyester carbonate.

Example 3 The same operation as in Example 1 was performed, except that bis (3-phenyl-4-hydroxyphenyl) sulfone was used instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, A polyester carbonate having the following repeating unit was obtained.

The reduced viscosity [ηsp / c] of the obtained polyester carbonate in methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C.
It was 0.61 dl / g.

The table shows the glass transition temperature, photoelastic coefficient, and moisture permeability of this polyester carbonate.

Comparative Example 1 The same operation as in Example 1 was performed, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane. A polyester carbonate having the following repeating unit was obtained.

The reduced viscosity [ηsp / c] of the obtained polyester carbonate in methylene chloride solution having a concentration of 0.5 g / dl at 20 ° C.
It was 0.56 dl / g.

The table shows the glass transition temperature, photoelastic coefficient, and moisture permeability of this polyester carbonate.

[Effects of the Invention] According to the present invention, transparency, mechanical strength, and heat resistance are excellent, the photoelastic coefficient is small, the anisotropy is small, the material is useful as a material for optical devices, and the water absorption is low. It is possible to provide a novel polyester carbonate which can be suitably used as a material for containers and the like, and its industrial value is great.

Claims (2)

(57) [Claims] (1) General formula And a general formula represented by In the repeating units (wherein, expressed, X is a single bond, an ether bond, a thioether bond, -SO ₂ -, Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n is 2
And p is an integer of 4 to 8. A novel polyester carbonate having a reduced viscosity [η _sp / c] of 0.3 to 2 dl / g at 20 ° C. in a methylene chloride solution having a concentration of 0.5 g / dl. 2. The general formula (Wherein X is a single bond, an ether bond, a thioether bond, -SO _2- , Wherein R ₁ and R ₂ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and n is 2
And p is an integer of 4 to 8. Wherein a bisphenol compound represented by the formula: is reacted with isophthalic acid halide and / or terephthalic acid halide and phosgene. And a general formula represented by Wherein X has the same meaning as described above, and the reduced viscosity [η _sp / c] at 20 ° C. of a methylene chloride solution having a concentration of 0.5 g / dl is 0.3 to 2.0 dl. / g New polyester carbonate production method.